93473-53-1Relevant academic research and scientific papers
Kinetics and Mechanism of Molecular A-Frame Formation in Reactions of (PF6)2 with Diazomethane, Carbon Monoxide, Sulfur Dioxide, Sulfur, and Hydrogen Chloride
Muralidharan, S.,Espenson, James H.
, p. 8104 - 8109 (1984)
The mechanism of the formation of A frames of the type (PF6)2 (Y = CH2, CO, S, SO2) from (PF6)2 by reaction with CH2N2, CO, S, and SO2 (R) in CH2Cl2 and other organic solvents has been investigated by using kinetic studies and product analysis.Pseudo-first-order kinetic data (excess 0) are consistent with either preequilibrium association of R with the complex prior to rate-limiting product formation or unimolecular formation of a common intermediate which is then attacked by R to form the A -frame product.Kinetic studies with 0 0 substantiate the latter.The most likely intermediate leading to the products is one with a dangling dppm ligand formed by Pt-P bond heterolysis.When 0 is very large, formation of this intermediate becomes rate limiting and is independent of the nature of R, with k = 2.73 +/-0.05E-2 s-1 (at 25 deg C; ΔH* = 25.0 kcal mol-1 and ΔS* = 18.5 cal mol-1 K-1).The same process and mechanism is observed for R = HCl, although with minor numerical differences; similar salt and solvent polarity effects occur in all of the reactions.
